Transparent base with transparent conductive film, method for producing same, and photoelectric converter comprising such base

ABSTRACT

The present invention provides a transparent substrate with a transparent conductive film that is thin but has a surface with concavities and convexities of increased height. A manufacturing method of the present invention includes a process of forming a transparent conductive film containing crystalline metal oxide as its main component on a transparent substrate by a pyrolytic oxidation method. In the method, a gaseous material containing a metal compound, an oxidizing material, and hydrogen chloride is supplied onto the transparent substrate. The process includes sequentially: a first step in which a mole ratio of the hydrogen chloride to the metal compound in the gaseous material is 0.5 to 5; and a second step in which the mole ratio is 2 to 10 and is higher than the mole ratio to be employed in the first step. With the present invention, a transparent substrate with a transparent conductive film can be provided that has a haze ratio of at least 15% and includes a transparent conductive film whose thickness is 300 nm to 750 nm.

TECHNICAL FIELD

The present invention relates to a transparent substrate with atransparent conductive film in which a transparent conductive film isformed on a transparent substrate, a method of manufacturing the same,and a photoelectric conversion element including the transparentsubstrate with a transparent conductive film as a member thereof.

BACKGROUND ART

Transparent substrates with a transparent conductive film that eachincludes a transparent substrate, such as glass, and a transparentconductive film formed thereon are used for photoelectric conversionelements, optical sensors, image displays, light emitting devices, etc.,with a functional thin film further being formed on the transparentconductive film. Examples of the image displays include liquid crystaldisplays, organic EL displays, and plasma displays. Examples of thelight emitting devices include field emission displays (FEDs), lightemitting diodes, and solid state lasers.

The transparent substrates with a transparent conductive film also areused as, for instance, window glass for buildings, window glass ofrefrigerators for stores, and document glass of copying machines,specifically Low-E (Low-Emissivity) glass, electromagnetic waveshielding glass, and defogging glass.

A photoelectric conversion element is an energy conversion element thatconverts optical energy into electric energy or vice versa. A solar cellconverts optical energy into electric energy. A solar cell with asilicon semiconductor thin film includes a configuration in which asilicon semiconductor film (a photoelectric conversion layer) with aphotoelectric conversion function and a back electrode film are formedsequentially on the transparent conductive film of a transparentsubstrate with a transparent conductive film.

Sunlight that has entered the transparent substrate with a transparentconductive film from the transparent substrate side passes through thetransparent conductive film to reach the photoelectric conversion layer.Electric energy produced in the photoelectric conversion layer is takenout through the transparent conductive film and the back electrode film.

In order to improve the sunlight conversion efficiency, it is desirableto increase the amount of light that reaches the photoelectricconversion layer. An effect of improving the conversion efficiency alsois provided when concavities and convexities are formed at the surfaceof the transparent conductive film to confine light in the photoelectricconversion layer. Many experiments and proposals have been made withrespect to the techniques for forming concavities and convexities at thesurface of the transparent conductive film.

JP61(1986)-288314A and JP61(1986)-288473A each disclose a technique forforming concavities and convexities by chemically etching the surface ofa transparent conductive film. This technique, however, results in lowerproductivity since it is necessary to employ additional processes suchas an etching process, a process for removing an etchant by waterwashing, a drying process to be carried out after the water washing,etc.

WO03/36657 discloses a technique for forming a first undercoating layerthat is tin oxide formed in a discontinuous dome shape, a secondundercoating layer that is a continuous silicon oxide film, and acontinuous tin oxide conductive film on a transparent substrate in thisorder. However, when this technique is used to form concavities andconvexities with a height of at least 200 nm, unevenness in haze iscaused that can be observed visually. The substrate with a transparentconductive film formed using a dome-shaped undercoating still issusceptible to improvement.

JP5(1993)-67797A discloses a transparent conductive substrate for solarcells that includes a crystalline tin oxide film formed of two layers ona glass sheet. In this substrate, tin oxide of the lower layer isoriented in a (110) plane while tin oxide of the upper layer is orientedin a (200) plane. FIG. 16 of JP5(1993)-67797A shows the relationshipbetween the thickness of the lower layer and the haze ratio of the wholefilm. According to this figure, the haze ratio of the whole film is nothigher than about 10%.

DISCLOSURE OF THE INVENTION

Generally, in a crystalline metal oxide film, crystal grains of metaloxide are grown and thereby concavities and convexities present at thesurface of the film increase in size. However, when the crystal grainssimply are grown, the thickness of the transparent conductive filmincreases to deteriorate the transparency of the film while the adhesionof the film to the substrate deteriorates due to the residual stress ofthe transparent conductive film.

The present invention is intended to provide a new manufacturing methodthat is used suitably for obtaining a transparent substrate with atransparent conductive film that is thin but has a surface withconcavities and convexities of increased height (that is, a higher hazeratio). Furthermore, the present invention also is intended to provide anew transparent substrate with a transparent conductive film that can bemanufactured by the above-mentioned method, and a photoelectricconversion element including the transparent substrate as a memberthereof.

The manufacturing method of the present invention includes a process offorming a transparent conductive film containing crystalline metal oxideas its main component on a transparent substrate by a pyrolyticoxidation method. In the pyrolytic oxidation method, a gaseous materialcontaining a metal compound, an oxidizing material, and hydrogenchloride is supplied onto the transparent substrate. The processincludes sequentially: a first step in which a mole ratio of thehydrogen chloride to the metal compound in the gaseous material is 0.5to 5; and a second step in which the mole ratio is 2 to 10 and is higherthan the mole ratio to be employed in the first step.

The substrate with a transparent conductive film of the presentinvention includes a transparent substrate and a transparent conductivefilm that is formed on the transparent substrate and that containscrystalline metal oxide as its main component. In the substrate, thetransparent conductive film has a thickness of 300 nm to 750 nm. Thetransparent substrate with a transparent conductive film has a hazeratio of at least 15%.

Furthermore, the present invention also provides a photoelectricconversion element including the above-mentioned transparent substratewith a transparent conductive film.

In the present invention, the mole ratio of the hydrogen chloride to themetal compound in the gaseous material is controlled in the process offorming a transparent conductive film containing crystalline metal oxideas its main component. In addition, the present invention employs atleast two gaseous materials that are different in the mole ratio fromeach other. When the ratio of the hydrogen chloride is controlledsuitably in the gaseous material, a substrate with a transparentconductive film can be obtained that has a haze ratio of at least 15%even when the transparent conductive film is as thin as 300 nm to 750nm. This substrate is excellent in optical transparency and provides agreat effect of scattering light at the surface of the transparentconductive film. The efficient use of characteristics of this substratemakes it possible to obtain a transparent substrate with a transparentconductive film that is excellent in not only optical transparency andoptical scattering but also conductivity.

Hence, in the photoelectric conversion element of the present invention,a smaller amount of incident light is absorbed by the transparentsubstrate with a transparent conductive film and therefore the incidentlight tends to become scattered light to reach a photoelectricconversion layer. Furthermore, the photoelectric conversion layer has agreat optical confinement effect, which improves the efficiency of usingincident sunlight. In addition, the photoelectric conversion element ofthe present invention includes a thin transparent conductive film.Accordingly, it has a high adhesion between the transparent conductivefilm and the transparent substrate and therefore is excellent in longterm stability.

When the transparent conductive film is formed, with the mole ratio ofthe hydrogen chloride to the metal compound being controlled, the formof crystals of the transparent conductive film can be controlled into apreferable state. This makes it easier to obtain a substrate with atransparent conductive film that is thin but allows a high haze ratio tobe obtained and that prevents unevenness in haze from occurring.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is a cross-sectional view showing an example of the photoelectricconversion element according to the present invention.

FIG. 2 is a diagram showing the configuration of an example of theapparatus that is used for manufacturing the transparent substrate witha transparent conductive film of the present invention by the so-called“on-line CVD method”.

FIG. 3 is a view showing the state of the cross section of thetransparent substrate with a transparent conductive film obtained inExample 1, which was observed with a scanning electron microscope (SEM)at an inclination of 10° with respect to the surface of the transparentsubstrate with a transparent conductive film.

FIG. 4 is a view showing the state of the cross section of thetransparent substrate with a transparent conductive film obtained inExample 3, which was observed with the SEM at an inclination of 10° withrespect to the surface of the transparent substrate with a transparentconductive film.

FIG. 5 is a view showing the state of the cross section of thetransparent substrate with a transparent conductive film obtained inExample 7, which was observed with the SEM at an inclination of 10° withrespect to the surface of the transparent substrate with a transparentconductive film.

FIG. 6 is a view showing the state of the cross section of thetransparent substrate with a transparent conductive film obtained inComparative Example 1, which was observed with the SEM at an inclinationof 10° with respect to the surface of the transparent substrate with atransparent conductive film.

FIG. 7 is a histogram with respect to elevation angles of convexitiespresent at the surface of the transparent conductive film obtained inExample 7.

FIG. 8 is a histogram with respect to elevation angles of convexitiespresent at the surface of the transparent conductive film obtained inComparative Example 2.

BEST MODE FOR CARRYING OUT THE INVENTION

The transparent conductive film contains crystalline metal oxide as itsmain component. In this case, the crystalline metal oxide denotes metaloxide whose X-ray diffraction pattern has peaks of its crystals.Examples of the metal oxide include indium oxide, indium oxide dopedwith tin, titanium oxide, tin oxide, and tin oxide doped with fluorineor antimony. However, a metal oxide film containing titanium oxide ortin oxide as its main component has advantages that it has excellentchemical resistance and can be formed using inexpensive raw materials.Preferable transparent conductive films include a tin oxide film dopedwith fluorine.

In this specification, an expression, “containing a component as a maincomponent” denotes that the content by percentage of the concernedcomponent is at least 50 wt %, as is used commonly. The content bypercentage of the concerned component is preferably at least 70 wt %,more preferably at least 90 wt %.

The transparent conductive film has a thickness of 300 nm to 750 nm,preferably 450 nm to 750 nm. When the thickness of the film exceeds 750nm, the magnitude of adhesion of the film may be lower than thatrequired practically, due to the residual stress of the film. On theother hand, when the film is thinner than 300 nm, the haze ratio to beobtained is not high and thereby the light scattering effect to beobtained is not sufficiently great.

In the transparent substrate with a transparent conductive film of thepresent invention, with respect to the peak area corresponding to theplane (orientation plane) in which crystalline oxide is oriented, whichis calculated from the X-ray diffraction pattern, when the peak area ofthe (110) plane is set at 100, it is advantageous to form thetransparent conductive film, with crystal growth being controlled sothat the peak areas of all the orientation planes other than the (110)plane are preferably 80 or smaller, more preferably 70 or smaller. A tinoxide film tends to be obtained that is thinner but has concavities andconvexities of increased height with an increase in the extent to whichcrystalline metal oxide is oriented in the (110) plane preferentiallyover the other orientation planes. It is further preferable that the(211) plane have the largest peak area after the (110) plane (that is tosay, the (211) plane has the second largest peak area).

Generally, the transparent conductive film is formed on the transparentsubstrate by a so-called physical vapor deposition method, such as asputtering method, a vacuum deposition method, etc., or a chemicaldeposition method involving a pyrolytic oxidation reaction, such as aspray method, a chemical vapor deposition method (a CVD method), etc.

In the present invention, the transparent substrate with a transparentconductive film is manufactured using the CVD method. In the CVD method,gaseous materials are decomposed with the thermal energy of ahigh-temperature transparent substrate.

A suitable metal compound to be added to a gaseous material to producecrystalline metal oxide that forms the transparent conductive film ischloride, specifically, organic metal chloride or inorganic metalchloride. When organic metal chloride is used, carbide that is producedthrough the pyrolytic reaction remains in the film to hinder the filmfrom having high transparency and further an organic component that isproduced subsidiarily becomes a factor of imposing a load on theenvironment. Hence, it is advantageous to use inorganic metal chlorideas the metal compound to be added to the gaseous material. Tin oxidethat is a preferable metal oxide can be obtained using a tin compound asthe metal compound.

Examples of the inorganic metal chloride include indium chloride, zincchloride, titanium chloride, and tin chloride (stannous chloride orstannic chloride (tin tetrachloride)). When consideration is given tothe chemical resistance of the metal oxide to be produced, the cost ofraw materials, etc, titanium chloride and tin chloride are preferable,and tin tetrachloride is particularly preferable as the tin chloride.

Examples of the oxidizing material to be added to the gaseous materialsinclude oxygen, water, water vapor, and dry air. Preferably, water vaporis used.

When inorganic metal chloride, particularly tin tetrachloride, and watervapor are mixed together, the oxidation reaction progresses rapidly toproduce solid tin oxide, and it may accumulate inside a pipe forsupplying the gaseous material to block the pipe. In addition, even ifthe gaseous material can be supplied, probably the composition of thegaseous material may vary and thereby the adhesion between thetransparent substrate and the transparent conductive film maydeteriorate.

Hydrogen chloride serves to prevent the oxidation reaction fromoccurring between tin tetrachloride and water vapor. Hence, when thepyrolytic oxidation reaction progresses in an atmosphere includinghydrogen chloride, the transparent conductive film can be formed stablyon the transparent substrate. It is advantageous to add hydrogenchloride to at least one of tin tetrachloride and water vapor that havenot been mixed together yet or both of them.

In the manufacturing method of the present invention, the transparentconductive film is formed through the process of forming a transparentconductive film that includes at least: a first step in which the moleratio of the hydrogen chloride to the metal compound is 0.5 to 5,preferably 0.8 to 5, and more preferably 1 to 5; and a second step inwhich the mole ratio is 2 to 10 and is higher than the mole ratio to beemployed in the first step. The mole ratio to be employed in the firststep is preferably lower than 4, more preferably 3 or lower, while themole ratio to be employed in the second step is preferably at least 3.

In the first step, a lot of crystalline initial grains are formed on thetransparent substrate due to the lower mole ratio of the hydrogenchloride. In the second step, crystals of the metal oxide grow, with thecrystalline initial grains serving as starting points. In the firststep, the amount and size of the crystalline initial grains can beadjusted by adjusting the above-mentioned mole ratio. In the first step,it is preferable that a very thin metal oxide film be formed and anumber of initial grains be formed. In the second step, a gaseousmaterial in which the above-mentioned mole ratio is relatively high issupplied to promote the growth of crystals of the metal oxide using theinitial grains as starting points and thereby crystals that are large indiameter and long in the thickness direction can be formed.

The process of forming a transparent conductive film further may includea third step after the second step. In this case, the mole ratio of thehydrogen chloride to the metal compound that is employed in the thirdstep can be determined according to a desirable crystal growth rate.Basically, the crystal growth rate can be adjusted suitably according tothe type of metal, the diameter and length of crystals to be obtained,etc. When a high growth rate is desirable, it is preferable that theabove-mentioned mole ratio to be employed in the third step be set at alower ratio than the above-mentioned ratio to be employed in the secondstep and further be set at a lower ratio than the above-mentioned ratioto be employed in the first step, specifically lower than 1.5 andpreferably lower than 1. In the present invention, the hydrogen chlorideis used to prevent the metal oxide from reacting in the gaseous materialin the first and second steps. Hence, it is preferable that in the thirdstep, the above-mentioned mole ratio is controlled to be in the rangedescribed above to promote crystal growth and thereby a desirable filmthickness be obtained.

The process of forming a transparent conductive film further may includea fourth step and a fifth step that are employed suitably after thethird step. In the case of growing crystals through a plurality of stepsafter the second step, as in the above, it is preferable that the moleratios of the hydrogen chloride to the metal compound to be employed insuch a plurality of steps be adjusted so as to be as low as describedabove, as a whole, for instance, to be lower as a whole than theabove-mentioned mole ratio that is employed in the second step.

Crystals of metal oxide such as tin oxide grow into a shape of pillarand the growth is accompanied by an increase in grain diameter.Accordingly, the number of initial grains is preferably small in orderto form tin oxide crystals with large diameters. However, an excessivelysmall number of initial grains results in appearance of huge crystals inthe second step. The huge crystals then may cause spots and stains andfurther may cause partial unevenness in haze.

With the method described above, crystalline metal oxide that isoriented in the (110) plane preferentially can be formed on thetransparent substrate. Furthermore, the transparent conductive film isobtained in which pillar-shaped crystals with large grain sizes thathave grown from the vicinity of the surface of the transparent substrateare in close contact with each other. Hence, even if the transparentconductive film is thinner, a high haze ratio can be maintained.

In the film in which crystals with large grain sizes that have grownfrom the vicinity of the surface of the transparent substrate are inclose contact with each other, the number of grain boundaries decreases.The decrease in the number of grain boundaries that cause scattering ofcarriers allows the mobility of the carriers to improve. Accordingly,even when the transparent conductive film is thinner, excellentconductivity can be maintained. Since the transparency can be improved,with the conductivity being maintained, this transparent substrate witha transparent conductive film can contribute to the improvement inefficiency of converting sunlight in a photoelectric conversion element.

In order to improve the conductivity of the transparent conductive filmcontaining tin oxide as its main component, the transparent conductivefilm can be doped with a small amount of fluorine. Examples of thefluorine compound to be added to the gaseous material include hydrogenfluoride, difluoroethane, chlorodifluoromethane, trifluoroacetic acid,and bromotrifluoromethane. However, hydrogen fluoride that is free fromorganic materials is preferable.

The gaseous material is prepared typically by mixing tin tetrachloride,an oxidizing material, hydrogen chloride, a fluorine-containingcompound, and a gaseous diluent together and then is supplied onto thetransparent substrate. When those raw materials are not mixed togetherwell, unevenness in composition and unevenness in thickness of the filmtend to be caused due to the unevenness in the composition of thegaseous material. The respective components of the gaseous material needto be in a gaseous state after being mixed together but can be liquid orsolid before being mixed together as long as they can be suppliedquantitatively.

The pyrolytic oxidation reaction progresses on the transparent substrateheated to a high temperature. Preferably, the surface temperature of thetransparent substrate is 400° C. to 800° C., particularly at least 600°C. When the transparent substrate has a surface temperature of at least600° C., the metal oxide thin film that has been formed is crystallizedeasily. Thereby conductivity improves and the rate at which the metaloxide thin film grows increases.

The CVD method involving the pyrolytic oxidation of the gaseous materialcan be carried out, for instance, as follows: a transparent substratethat has been cut into a predetermined size is placed on a mesh belt topass through a heating furnace, and when the temperature of thetransparent substrate reaches a predetermined temperature, the gaseousmaterial is supplied. It, however, is preferable that the CVD method bethe so-called on-line CVD method in which the transparent substrate is aglass ribbon located on a molten metal bath in a process ofmanufacturing glass by the float glass process, particularly a glassribbon whose surface temperature is at least 600° C. With this method, ahigh temperature state of the transparent substrate can be obtainedeasily and it is possible to obtain a transparent substrate with atransparent conductive film without supplying additional energy forheating the transparent substrate to a high temperature.

The on-line CVD method in which a gaseous material containing hydrogenchloride mixed thereinto is used makes it possible to manufacture alarge-area transparent substrate with a transparent conductive filmstably and continuously for a long period of time at a higher speed.

The transparent conductive film may be formed directly on thetransparent substrate. However, at least one undercoating layer,preferably two undercoating layers, may be provided on the transparentsubstrate beforehand and then the transparent conductive film may beformed thereon. The undercoating layer(s) prevents the occurrence ofphenomena that can be caused due to the combination of the transparentsubstrate and the transparent conductive film and that should beavoided. An example of such phenomena is a phenomenon that an alkalinecomponent diffuses from glass that is the transparent substrate to lowerthe conductivity of the transparent conductive film.

The undercoating layer(s) also can provide unique advantageousfunctions, for instance, a function of reducing the amount of lightreflected by the interface between the transparent substrate and themetal oxide film, and a function of improving the adhesion between thetransparent substrate and the metal oxide film. The undercoatinglayer(s) may consist of a plurality of layers according to the purposeof providing it(them).

When one undercoating layer is employed, it is preferably a film thathas a thickness of 40 nm to 120 nm and is formed of a material whoserefractive index is 1.5 to 1.8. An example of the material whoserefractive index is in the above-mentioned range is silicon oxycarbide.When two undercoating layers are employed, preferably a firstundercoating layer located on the transparent substrate side is a filmthat has a thickness of 10 nm to 100 nm and is formed of a materialwhose refractive index is 1.6 to 2.4 while a second undercoating layerlocated on the transparent conductive film side is a film that has athickness of 10 nm to 100 nm and is formed of a material whoserefractive index is 1.4 to 1.8. Examples of the material whoserefractive index is 1.6 to 2.4 include tin oxide, indium oxide, and zincoxide. Examples of the material whose refractive index is 1.4 to 1.8include silicon oxide, aluminum oxide, and silicon oxycarbide.

The method of forming the undercoating layer(s) is not particularlylimited. However, when the same method as that employed for forming thetransparent conductive film is used for forming the undercoatinglayer(s), the control of the whole processes of manufacturing thetransparent substrate with a transparent conductive film is facilitated.Among others an on-line CVD method is particularly preferable in which alayer and a metal oxide film are formed successively by the same method.

When glass containing an alkaline component is used as the transparentsubstrate, it is advantageous that an alkali barrier layer that servesas a barrier to the alkaline component, such as a silicon oxide film, asilicon oxycarbide film, etc., is formed as the undercoating layer so asto prevent the alkaline component from diffusing into the transparentconductive film. In order to bond the transparent substrate and thealkali barrier layer to each other with higher strength, it is furtherpreferable that a metal oxide undercoating layer be interposedtherebetween.

Examples of the silicon material to be used in forming a silicon oxidefilm by the pyrolytic oxidation method include monosilane, disilane,trisilane, monochlorosilane, dichlorosilane, dimethylsilane,trimethylsilane, and tetramethyl disilane. Among others monosilane isparticularly preferable. Examples of the oxidizing material to be usedin this case include oxygen, water, water vapor, dry air, carbondioxide, carbon monoxide, and nitrogen dioxide. Among others oxygen isparticularly preferable. When monosilane is used as the siliconmaterial, an unsaturated hydrocarbon gas such as ethylene, acetylene,toluene, etc. may be added to control the reaction between themonosilane and the oxidizing material and to control the refractiveindex of the film to be obtained.

A metal oxide film may be formed between the silicon oxide film and thetransparent substrate to strengthen the adhesion therebetween and toreduce the amount of light reflected at the interface therebetween. Inthis case, the use of the same type of metal compound as that to be usedfor forming the transparent conductive film facilitates the control ofthe whole process. Preferably, this film also is formed by the samemethod as that employed in forming the transparent conductive film,particularly the on-line CVD method. When this metal oxide film is a tinoxide film, it is not necessary to add hydrogen chloride to the gaseousmaterial to be used for forming the tin oxide film.

The photoelectric conversion element can be obtained by forming aphotoelectric conversion layer and a back electrode layer sequentiallyon a transparent substrate with a transparent conductive film accordingto a well-known method. FIG. 1 shows a cross-sectional view of anexample of the photoelectric conversion element. In this photoelectricconversion element, a substrate with a transparent conductive film iscomposed of a transparent substrate 20, a first undercoating layer 21, asecond undercoating layer 22, and a transparent conductive film 23, andfurther a photoelectric conversion layer 24 and a back electrode film 25are formed on the transparent conductive film 23.

Preferably, the photoelectric conversion layer 24 is formed of layers ofphotoreactive semiconductor thin films that absorb received light toproduce photocarriers. The photoelectric conversion layer to be used ingeneral is formed of layers of amorphous-silicon-based semiconductorthin films, layers of non-single-crystal-silicon-based crystallinesemiconductor thin films, or layers of semiconductor thin films that area combination thereof. It is preferable that specifically, a p-typesilicon semiconductor film, an i-type silicon semiconductor film, and ann-type silicon semiconductor film be stacked in this order from thetransparent substrate side to form a silicon-based semiconductorphotoelectric conversion layer with a multilayered structure.

Generally, a metal thin film is used for the back electrode film 25. Ametal oxide thin film may be formed between the n-type silicon film andthe back electrode film to prevent the silicon film and the metal thinfilm (the back electrode film) from being alloyed and thereby to improvethe functional stability of both the films.

The surface shape of the transparent conductive film affects thephotoelectric conversion efficiency of the photoelectric conversionlayer. Excessively large elevation angles of convexities present at thesurface of the transparent conductive film result in an increase in thenumber of lattice defects of pn(pin) junctions in the photoelectricconversion layer. In addition, when the convexities have large elevationangles and the concavities present at the film surface have steepgradients, a short-circuit current (Jsc) decreases. Furthermore, whenthe convexities have large elevation angles and thereby have sharp peaksand steep ridgelines, an open circuit voltage (Voc) decreases. On theother hand, excessively small elevation angles of the convexities resultin a decrease in haze ratio of the transparent substrate with atransparent conductive film and thereby a sufficiently great opticalconfinement effect cannot be obtained. With consideration given to theabove, the average (the elevation angle average) of elevation angles ofthe convexities present at the surface of the transparent conductivefilm is preferably 20 degrees to 30 degrees.

The haze ratio of the transparent substrate with a transparentconductive film also is affected by the diameters of convexities of thetransparent conductive film. From this point of view, the average (theconvexity diameter average) of diameters of the convexities present atthe surface of the transparent conductive film is preferably 300 nm to500 nm.

It is preferable that the surface of the transparent conductive filminclude no dome-shaped convexities that project locally. This is becausethe presence of such convexities results in unevenness in haze thattends to develop in the transparent substrate with a transparentconductive film.

FIG. 2 is a conceptual diagram showing an example of the apparatus to beused in the on-line CVD method. A glass material is poured from amelting furnace (a float furnace) 11 into a float bath 12 to be formedinto a glass ribbon 10. The glass ribbon 10 moves on a molten tin bath15 to become semisolid. Thereafter, this is lifted with a roller 17 andthen is carried into an annealing furnace 13. The glass ribbonsolidified in the annealing furnace 13 is cut into a glass sheet with apredetermined size using a cutting device, which is not shown in thefigure.

The float bath 12 includes a predetermined number of coaters 16 (threecoaters 16 a, 16 b, and 16 c in the embodiment shown in the figure) thatare disposed over the molten tin bath 15 at a predetermined distancefrom the surface of the glass ribbon 10 whose temperature is high. Thesecoaters supply gaseous materials and thereby, an undercoating film and atransparent conductive film are formed successively on the glass ribbon10 in this order. In the method of manufacturing a transparent substratewith a transparent conductive film of the present invention, when oneundercoating layer is to be formed first and then a transparentconductive film is to be formed through two processes, the undercoatinglayer is formed with the coater 16 a located on the furthest upstreamside in the float bath and then the transparent conductive film isformed using the coaters 16 b and 16 c.

When at least four coaters 16 are disposed, the transparent substratewith a transparent conductive film can be formed of a plurality ofundercoating layers and an increased number of transparent conductivefilms. Moreover, after the glass ribbon 10 provided with the respectivefilms formed on the surface thereof comes out of the float bath 12, anadditional thin film may be formed on the glass ribbon 10 by a spraymethod.

Hereafter, the present invention is described using examples but is notlimited by the following examples.

The following descriptions are directed to the methods of measurementand evaluation of properties that are used in the descriptions of theexamples.

Haze Ratio

Light is allowed to enter a transparent substrate with a transparentconductive film from the transparent substrate side and thereby the hazeratio was measured using NDH2000 manufactured by Nippon Denshoku.

Sheet Resistance

The sheet resistance was measured using a MCP-TESTER LORESTA-FPmanufactured by Dia Instruments.

Peak Area

The peak area of each orientation plane was determined by multiplyingthe diffraction peak intensity of each orientation plane by thehalf-value width of the peak, wherein the diffraction peak intensity wasobserved in an X-ray diffraction pattern of crystals that was obtainedusing a RAD-RC apparatus manufactured by RIGAKU Corporation.Subsequently, the ratio of the peak area of each orientation plane tothat of the (110) plane was calculated, with the peak area of the (110)plane being set at 100.

Elevation Angle Average

With an AFM (an atomic force microscope; a scanning probe microscopemanufactured by THERMOMICROSCOPE), concavities and convexities that arepresent at the surface of a transparent conductive film were measured ina non-contact mode. Angles that each are formed between the ridge lineof a convexity and the sample stage of the microscope were measured aselevation angles and then the average of the elevation angles wasdetermined.

Convexity Diameter Average

A plan view that showed a transparent substrate with a transparentconductive film viewed from the direction perpendicular to the surfaceof the transparent conductive film was prepared based on the dataobtained by the measurement carried out using the AFM. Thereafter theareas of the convexities that appeared in the plan view were calculatedand then the average of diameters of circles that had the same areas asthose of the convexities was calculated.

Thickness of Transparent Conductive Film

A predetermined region of a transparent conductive film was etched usingZn powder and hydrochloric acid and then the height of steps thus formedwas measured using a surface profiler (AlphaStep-500 manufactured byTencor). The surface of the transparent conductive film was consideredas a surface in which the concavities and convexities present at thesurface were averaged.

EXAMPLE 1

An undercoating film and a transparent conductive film (a crystallinemetal oxide film) were formed sequentially on a glass ribbon using theon-line CVD method. Specifically, 98 vol. % of nitrogen and 2 vol. % ofhydrogen were supplied into the float bath while the inside of the floatbath was maintained at a slightly higher pressure than that of theoutside thereof. With the inside of the float bath being maintained in anonoxidative atmosphere, a mixed gas consisting of tin tetrachloride(vapor), water vapor, hydrogen chloride, nitrogen, and helium wassupplied from a first coater located on the furthest upstream side.Thereby a 55-nm thick tin oxide film (a SnO₂ film; a first undercoatinglayer) with a refractive index of 1.9 was formed on the glass ribbon.Subsequently, a mixed gas consisting of monosilane, ethylene, oxygen,and nitrogen was supplied from a second coater and thereby a 30-nm thicksilicon oxide film (a SiO₂ film; a second undercoating layer) with arefractive index of 1.46 was formed on the first undercoating layer.Further, a mixed gas consisting of 0.58 mol % of tin tetrachloride(vapor), 11.65 mol % of water vapor, 0.70 mol % of hydrogen chloride,and nitrogen (the rest; the same holds true in the followingdescriptions, i.e. nitrogen accounts for the rest) was supplied from athird coater. Thus a first tin oxide film was formed on the secondundercoating layer. Furthermore, a mixed gas consisting of 1.87 mol % oftin tetrachloride (vapor), 37.39 mol % of water vapor, 9.35 mol % ofhydrogen chloride, and nitrogen was supplied from a fourth coater thatwas disposed on the further downstream side. Thereby a second tin oxidefilm was formed on the first tin oxide film. Subsequently, a mixed gasconsisting of 3.40 mol % of tin tetrachloride (vapor), 50.99 mol % ofwater vapor, 0.68 mol % of hydrogen chloride, 1.19 mol % of hydrogenfluoride, and nitrogen was supplied from a fifth coater located on thefurthest downstream side. Thereby a tin oxide film doped with fluorine(a SnO₂:F film) was formed on the second tin oxide film. Thus atransparent substrate with a transparent conductive film was obtained.The thickness of the transparent conductive film, i.e. the total of thethicknesses of the first tin oxide film, the second tin oxide film, andthe tin oxide film doped with fluorine was 700 nm. The transparentsubstrate with a transparent conductive film thus obtained had a hazeratio of 19.5%. The transparent conductive film had a sheet resistanceof 9.5 Ω/□. With respect to the peak areas of crystals, the peak area ofthe (211) plane was 43 and the peak areas of other orientation planeswere further smaller than that.

EXAMPLE 2

A transparent substrate with a transparent conductive film was obtainedin the same manner as in Example 1 except that the gaseous material tobe supplied from the fourth coater was a mixed gas consisting of 1.61mol % of tin tetrachloride (vapor), 16.11 mol % of water vapor, 4.83 mol% of hydrogen chloride, and nitrogen. The thickness of the transparentconductive film was 720 nm. The transparent substrate with a transparentconductive film thus obtained had a haze ratio of 28.0%. The transparentconductive film had a sheet resistance of 10.2 Ω/□. With respect to thepeak areas of crystals, the peak area of the (211) plane was 38 and thepeak areas of other orientation planes were further smaller than that.

EXAMPLE 3

A transparent substrate with a transparent conductive film was obtainedin the same manner as in Example 2 except that the amount of thehydrogen chloride contained in the mixed gas to be supplied from thethird coater was 1.40 mol %. The thickness of the transparent conductivefilm was 687 nm. The transparent substrate with a transparent conductivefilm thus obtained had a haze ratio of 36.9%. The transparent conductivefilm had a sheet resistance of 12.7 Ω/□. With respect to the peak areasof crystals, the peak area of the (211) plane was 26 and the peak areasof other orientation planes were further smaller than that.

EXAMPLE 4

An undercoating film and a transparent conductive film (a crystallinemetal oxide film) were formed sequentially on a glass ribbon using theon-line CVD method. Specifically, 98 vol. % of nitrogen and 2 vol. % ofhydrogen were supplied into the float bath while the inside of the floatbath was maintained at a slightly higher pressure than that of theoutside thereof. With the inside of the float bath being maintained in anonoxidative atmosphere, a mixed gas consisting of tin tetrachloride(vapor), water vapor, hydrogen chloride, nitrogen, and helium wassupplied from the first coater located on the furthest upstream side.Thereby a 55-nm thick tin oxide film (a SnO₂ film; a first undercoatinglayer) with a refractive index of 1.9 was formed on the glass ribbon.Subsequently, a mixed gas consisting of monosilane, ethylene, oxygen,and nitrogen was supplied from the second coater and thereby a 30-nmthick silicon oxide film (a SiO₂ film; a second undercoating layer) witha refractive index of 1.46 was formed on the first undercoating layer.Further, a mixed gas consisting of 0.50 mol % of tin tetrachloride(vapor), 14.88 mol % of water vapor, 0.60 mol % of hydrogen chloride,and nitrogen was supplied from the third coater. Thus a first tin oxidefilm was formed on the second undercoating layer. Furthermore, a mixedgas consisting of 1.49 mol % of tin tetrachloride (vapor), 14.91 mol %of water vapor, 10.44 mol % of hydrogen chloride, and nitrogen wassupplied from the fourth coater that was disposed on the furtherdownstream side. Thereby a second tin oxide film was formed on the firsttin oxide film. Subsequently, a mixed gas consisting of 3.17 mol % oftin tetrachloride (vapor), 47.48 mol % of water vapor, 0.16 mol % ofhydrogen chloride, 0.55 mol % of hydrogen fluoride, and nitrogen wassupplied from the fifth coater located on the furthest downstream side.Thereby a tin oxide film doped with fluorine (a SnO₂:F film) was formedon the second tin oxide film. Thus a transparent substrate with atransparent conductive film was obtained. The thickness of thetransparent conductive film was 611 nm. The transparent substrate with atransparent conductive film thus obtained had a haze ratio of 15.5%. Thetransparent conductive film had a sheet resistance of 13.7 Ω/□. Withrespect to the peak areas of crystals, the peak area of the (211) planewas 67 and the peak areas of other orientation planes were furthersmaller than that.

EXAMPLE 5

An undercoating film and a transparent conductive film (a crystallinemetal oxide film) were formed sequentially on a glass ribbon using theon-line CVD method. Specifically, 98 vol. % of nitrogen and 2 vol. % ofhydrogen were supplied into the float bath while the inside of the floatbath was maintained at a slightly higher pressure than that of theoutside thereof. With the inside of the float bath being maintained in anonoxidative atmosphere, a mixed gas consisting of monosilane, ethylene,oxygen, and nitrogen was supplied from the first coater located on thefurthest upstream side. Thereby a 45-nm thick silicon oxycarbide film (aSiOC film; an undercoating layer) with a refractive index of 1.65 wasformed on the glass ribbon. Subsequently, a mixed gas of oxygen andnitrogen was sprayed thereon from the second coater. In this case, theoxygen concentration was 33 mol %. Further, a mixed gas consisting of0.35 mol % of tin tetrachloride (vapor), 7.06 mol % of water vapor, 0.64mol % of hydrogen chloride, and nitrogen was supplied from the thirdcoater. Thus a first tin oxide film was formed on the undercoatinglayer. Furthermore, the same mixed gases as those used in Example 2 weresupplied from the fourth and fifth coaters, respectively. Thus atransparent substrate with a transparent conductive film was obtained.The thickness of the transparent conductive film was 700 nm. Thetransparent substrate with a transparent conductive film thus obtainedhad a haze ratio of 16.5%. The transparent conductive film had a sheetresistance of 8.9 Ω/□. With respect to the peak areas of crystals, thepeak area of the (211) plane was 41 and the peak areas of otherorientation planes were further smaller than that.

EXAMPLE 6

Non-alkali glass that had been precut into a square with a size of 10cm×10 cm was washed and then was dried. In a belt furnace, a 55-nm thicktin oxide film (a first undercoating layer) with a refractive index of1.9 was formed on the glass sheet that had been washed and dried.Subsequently, a 30-nm thick silicon oxide film (a second undercoatinglayer) with a refractive index of 1.46 was formed on the firstundercoating layer. Furthermore, a mixed gas consisting of 0.30 mol % oftin tetrachloride (vapor), 9.30 mol % of water vapor, 0.78 mol % ofhydrogen chloride, and nitrogen was supplied. Thus a first tin oxidefilm was formed on the second undercoating layer. Subsequently, a mixedgas consisting of 0.30 mol % of tin tetrachloride (vapor), 9.30 mol % ofwater vapor, 2.35 mol % of hydrogen chloride, and nitrogen was supplied.Thereby a second tin oxide film was formed on the first tin oxide film.Thereafter, a mixed gas consisting of 2.50 mol % of tin tetrachloride(vapor), 67.50 mol % of water vapor, 0.40 mol % of hydrogen chloride,1.40 mol % of hydrogen fluoride, and nitrogen was supplied. Thereby afirst tin oxide film doped with fluorine was formed on the second tinoxide film. Thus a transparent substrate with a transparent conductivefilm was obtained. The thickness of the transparent conductive film was740 nm. The transparent substrate with a transparent conductive filmthus obtained had a haze ratio of 25.5%. The transparent conductive filmhad a sheet resistance of 11.5 Ω/□. With respect to the peak areas ofcrystals, the peak area of the (211) plane was 55 and the peak areas ofother orientation planes were further smaller than that.

EXAMPLE 7

A first undercoating layer and a second undercoating layer were formedin the same manner as in Example 6. Further, a mixed gas consisting of2.30 mol % of tin tetrachloride (vapor), 29.90 mol % of oxygen, 1.84 mol% of hydrogen chloride, and nitrogen was supplied. Thereby a first tinoxide film was formed on the second undercoating layer. Subsequently, amixed gas consisting of 0.30 mol % of tin tetrachloride (vapor), 9.30mol % of water vapor, 2.35 mol % of hydrogen chloride, and nitrogen wassupplied. Thereby a second tin oxide film was formed on the first tinoxide film. Thereafter, a mixed gas consisting of 1.50 mol % of tintetrachloride (vapor), 45.0 mol % of water vapor, 1.1 mol % of hydrogenchloride, 1.38 mol % of hydrogen fluoride, and nitrogen was supplied.Thereby a tin oxide film doped with fluorine was formed on the secondtin oxide film. Thus a transparent substrate with a transparentconductive film was obtained. The thickness of the transparentconductive film was 740 nm. The transparent substrate with a transparentconductive film thus obtained had a haze ratio of 19.3%. The transparentconductive film had a sheet resistance of 9.9 Ω/□. With respect to thepeak areas of crystals, the peak area of the (211) plane was 38 and thepeak areas of other orientation planes were further smaller than that.

EXAMPLE 8

A transparent substrate with a transparent conductive film was obtainedin the same manner as in Example 3 except that: the gaseous materialsupplied from the third coater was a mixed gas consisting of 0.4 mol %of tin tetrachloride (vapor), 7.1 mol % of water vapor, 0.4 mol % ofhydrogen chloride, and nitrogen; the gaseous material supplied from thefourth coater was a mixed gas consisting of 2.3 mol % of tintetrachloride (vapor), 22.7 mol % of water vapor, 6.9 mol % of hydrogenchloride, and nitrogen; and the gaseous material supplied from the fifthcoater was a mixed gas consisting of 2.6 mol % of tin tetrachloride(vapor), 39.5 mol % of water vapor, 0.52 mol % of hydrogen chloride,1.12 mol % of hydrogen fluoride, and nitrogen. The thickness of thetransparent conductive film was 640 nm. The transparent substrate with atransparent conductive film thus obtained had a haze ratio of 18.8%. Thetransparent conductive film had a sheet resistance of 10.3 Ω/□. Withrespect to the peak areas of crystals, the peak area of the (211) planewas 44 and the peak areas of other orientation planes were not largerthan 28.

EXAMPLE 9

A transparent substrate with a transparent conductive film was obtainedin the same manner as in Example 3 except that: the gaseous materialsupplied from the third coater was a mixed gas consisting of 0.6 mol %of tin tetrachloride (vapor), 11.6 mol % of water vapor, 1.8 mol % ofhydrogen chloride, and nitrogen; the gaseous material supplied from thefourth coater was a mixed gas consisting of 2.4 mol % of tintetrachloride (vapor), 60.1 mol % of water vapor, 12.0 mol % of hydrogenchloride, and nitrogen; and the gaseous material supplied from the fifthcoater was a mixed gas consisting of 2.4 mol % of tin tetrachloride(vapor), 60.1 mol % of water vapor, 2.9 mol % of hydrogen chloride, 1.46mol % of hydrogen fluoride, and nitrogen. The thickness of thetransparent conductive film was 700 nm. The transparent substrate with atransparent conductive film thus obtained had a haze ratio of 22.5%. Thetransparent conductive film had a sheet resistance of 11.3 Ω/□. Withrespect to the peak areas of crystals, the peak area of the (211) planewas 32 and the peak areas of other orientation planes were not largerthan 17.

COMPARATIVE EXAMPLE 1

An undercoating film and a transparent conductive film (a crystallinemetal oxide film) were formed sequentially on a glass ribbon using theon-line CVD method. Specifically, 98 vol. % of nitrogen and 2 vol. % ofhydrogen were supplied into the float bath while the inside of the floatbath was maintained at a slightly higher pressure than that of theoutside thereof. With the inside of the float bath being maintained in anonoxidative atmosphere, a mixed gas consisting of tin tetrachloride(vapor), water vapor, hydrogen chloride, nitrogen, and helium wassupplied from the first coater located on the furthest upstream side.Thereby a 55-nm thick tin oxide film (a first undercoating layer) with arefractive index of 1.9 was formed on the glass ribbon. Subsequently, amixed gas consisting of monosilane, ethylene, oxygen, and nitrogen wassupplied from the second coater and thereby a 30-nm thick silicon oxidefilm (a second undercoating layer) with a refractive index of 1.46 wasformed on the first undercoating layer. Further, a mixed gas consistingof 0.90 mol % of tin tetrachloride (vapor), 27.06 mol % of water vapor,0.05 mol % of hydrogen chloride, and nitrogen was supplied from thethird coater. Thus a first tin oxide film was formed on the secondundercoating layer. Furthermore, a mixed gas consisting of 3.05 mol % oftin tetrachloride (vapor), 30.49 mol % of water vapor, 0.15 mol % ofhydrogen chloride, and nitrogen was supplied from the fourth coater thatwas disposed on the further downstream side. Thereby a second tin oxidefilm was formed on the first tin oxide film. Subsequently, a mixed gasconsisting of 2.92 mol % of tin tetrachloride (vapor), 43.78 mol % ofwater vapor, 0.58 mol % of hydrogen chloride, 0.23 mol % of hydrogenfluoride, and nitrogen was supplied from the fifth coater located on thefurthest downstream side. Thereby a tin oxide film doped with fluorinewas formed on the second tin oxide film. Thus a transparent substratewith a transparent conductive film was obtained. The thickness of thetransparent conductive film was 810 nm. The transparent substrate with atransparent conductive film thus obtained had a haze ratio of 14.5%. Thetransparent conductive film had a sheet resistance of 14.0 Ω/□. Withrespect to the peak areas of crystals, the peak area of the (211) planewas 118 and the peak areas of other orientation planes were not largerthan 94.

COMPARATIVE EXAMPLE 2

A transparent substrate with a transparent conductive film was obtainedin the same manner as in Example 3 except that: the gaseous materialsupplied from the third coater was a mixed gas consisting of 1.7 mol %of tin tetrachloride (vapor), 58.8 mol % of water vapor, 0.34 mol % ofhydrogen chloride, and nitrogen; the gaseous material supplied from thefourth coater was a mixed gas consisting of 3.2 mol % of tintetrachloride (vapor), 31.9 mol % of water vapor, 0.16 mol % of hydrogenchloride, and nitrogen; and the gaseous material supplied from the fifthcoater was a mixed gas consisting of 3.4 mol % of tin tetrachloride(vapor), 51.0 mol % of water vapor, 0.68 mol % of hydrogen chloride,1.19 mol % of hydrogen fluoride, and nitrogen. The thickness of thetransparent conductive film was 960 nm. The transparent substrate with atransparent conductive film thus obtained had a haze ratio of 25.8%. Thetransparent conductive film had a sheet resistance of 9.0 Ω/□. Withrespect to the peak areas of crystals, the peak area of the (211) planewas 153 and the peak areas of other orientation planes were not largerthan 88.

The results obtained in Examples 1 to 9 and Comparative Examples 1 and 2were summarized in Table 1. TABLE 1 Max. of Peak Areas ElevationConvexity HCl/SnCl₄ (Mole Ratio) Thickness Sheet Haze other than AngleDiameter First Second Third of TCF Resistance Ratio (110) AverageAverage Step Step Step (nm) (Ω/□) (%) Plane (°) (nm) Ex. 1 1.2 5.0 0.2700 9.5 19.5 43 27.5 378 Ex. 2 1.2 3.0 0.2 720 10.2 28.0 38 27.9 442 Ex.3 2.4 3.0 0.2 687 12.7 36.9 26 — — Ex. 4 1.2 7.0 0.05 611 13.7 15.5 67 —— Ex. 5 1.8 3.0 0.2 700 8.9 16.5 41 27.8 387 Ex. 6 2.6 7.8 0.16 740 11.525.5 55 — — Ex. 7 0.8 7.8 0.73 740 9.9 19.3 38 23.9 414 Ex. 8 1.0 3.00.2 640 10.3 18.8 44 27.6 370 Ex. 9 3.0 5.0 1.2 700 11.0 23.0 42 26.5419 C. Ex. 1 0.06 0.05 0.2 810 14.0 14.5 118  — — C. Ex. 2 0.2 0.03 0.2960 9.0 25.8 153  31.6 379* First Step, Second Step, and Third Step denote steps of forming afirst tin oxide film, a second tin oxide film, and a tin oxide filmdoped with fluorine, respectively.* The peak areas are relative values expressed with the peak area of the(110) plane being set at 100.* The elevation angle average and the convexity diameter average werenot measured in some samples.* In Table 1, “Ex.” and “C. Ex.” denote Example and Comparative Example,respectively.* In Table 1, “Thickness of TCF” indicates the thickness of thetransparent conductive film.

As shown in Table 1, the transparent substrates with a transparentconductive film obtained in Examples 1 to 9 each had a haze ratio of atleast 15% even when their transparent conductive films each had athickness of 750 nm or less. On the other hand, the haze ratio of thetransparent substrate with a transparent conductive film obtained inComparative Example 1 did not reach 15% even though the thickness of thetransparent conductive film exceeded 750 nm. The transparent substratewith a transparent conductive film obtained in Comparative Example 2 hada high haze ratio but this was simply because the transparent conductivefilm was thick. In the transparent substrates with a transparentconductive film obtained in Examples 1 to 9, the crystals of tin oxideforming the transparent conductive films are oriented in the (110) planepreferentially.

No dome-shaped convexities that projected locally were observed at thesurface of the transparent conductive film formed in each example (seeFIGS. 3 to 5).

In Examples 1 to 5 and 8 to 9 as well as Comparative Examples 1 and 2that were carried out using the on-line CVD method, the glass ribbon hada surface temperature of 620° C. to 690° C. in forming the transparentconductive film. In Examples 6 and 7, the temperature of the glass sheetwas about 660° C. in forming the transparent conductive film.

INDUSTRIAL APPLICABILITY

The transparent substrate with a transparent conductive film of thepresent invention are very useful as a member of photoelectricconversion elements such as solar cells, optical sensors, etc., displayssuch as liquid crystal displays, organic EL displays, plasma displays,etc., and light emitting devices such as FEDs, light emitting diodes,solid state lasers, etc.

1. A method of manufacturing a transparent substrate with a transparentconductive film, comprising a process of forming a transparentconductive film containing crystalline metal oxide as its main componenton a transparent substrate by a pyrolytic oxidation method, in themethod, a gaseous material containing a metal compound, an oxidizingmaterial, and hydrogen chloride being supplied onto the transparentsubstrate, wherein the process comprises sequentially: a first step inwhich a mole ratio of the hydrogen chloride to the metal compound in thegaseous material is 0.5 to 5; and a second step in which the mole ratiois 2 to 10 and is higher than the mole ratio to be employed in the firststep.
 2. The method of manufacturing a transparent substrate with atransparent conductive film according to claim 1, wherein the mole ratioto be employed in the first step is 1 to
 5. 3. The method ofmanufacturing a transparent substrate with a transparent conductive filmaccording to claim 1, further comprising a third step in which the moleratio is lower than that to be employed in the second step, after thesecond step.
 4. The method of manufacturing a transparent substrate witha transparent conductive film according to claim 3, wherein the moleratio to be employed in the third step is lower than 1.5.
 5. The methodof manufacturing a transparent substrate with a transparent conductivefilm according to claim 1, wherein the mole ratio to be employed in thefirst step is lower than 4, and the mole ratio to be employed in thesecond step is at least
 3. 6. The method of manufacturing a transparentsubstrate with a transparent conductive film according to claim 1,further comprising a process of forming at least one undercoating layeron the transparent substrate, before the first step.
 7. The method ofmanufacturing a transparent substrate with a transparent conductive filmaccording to claim 1, further comprising a process of forming twoundercoating layers on the transparent substrate, before the first step.8. The method of manufacturing a transparent substrate with atransparent conductive film according to claim 1, wherein thetransparent substrate is a glass ribbon having a surface temperature ofat least 600° C. located on a molten metal bath in a process ofmanufacturing glass by a float glass process.
 9. The method ofmanufacturing a transparent substrate with a transparent conductive filmaccording to claim 1, wherein the metal compound is a tin compound, andthe metal oxide is tin oxide.
 10. A transparent substrate with atransparent conductive film, comprising a transparent substrate and atransparent conductive film that is formed on the transparent substrateand that contains crystalline metal oxide as its main component, whereinthe transparent conductive film has a thickness of 300 nm to 750 nm, andthe transparent substrate with a transparent conductive film has a hazeratio of at least 15%.
 11. The transparent substrate with a transparentconductive film according to claim 10, wherein with respect to peakareas corresponding to orientation planes of the crystalline oxidecalculated from an X-ray diffraction pattern, when the peak area of a(110) plane is set at 100, all the orientation planes other than the(110) plane each have a peak area of 80 or smaller.
 12. The transparentsubstrate with a transparent conductive film according to claim 11,wherein a (211) plane has the largest peak area after the (110) plane.13. The transparent substrate with a transparent conductive filmaccording to claim 10, wherein the average of elevation angles ofconvexities present at a surface of the transparent conductive film is20 degrees to 30 degrees.
 14. The transparent substrate with atransparent conductive film according to claim 10, wherein the averageof diameters of convexities present at a surface of the transparentconductive film is 300 nm to 500 nm.
 15. The transparent substrate witha transparent conductive film according to claim 10, wherein thetransparent conductive film has a surface that includes no dome-shapedconvexities projecting locally.
 16. The transparent substrate with atransparent conductive film according to claim 10, wherein the metaloxide is tin oxide.
 17. The transparent substrate with a transparentconductive film according to claim 10, further comprising at least oneundercoating layer between the transparent substrate and the transparentconductive film.
 18. The transparent substrate with a transparentconductive film according to claim 10, further comprising twoundercoating layers between the transparent substrate and thetransparent conductive film.
 19. The transparent substrate with atransparent conductive film according to claim 18, wherein a firstundercoating layer located on a side of the transparent substrate has athickness of 10 nm to 100 nm and is formed of a material having arefractive index of 1.6 to 2.4 while a second undercoating layer locatedon a side of the transparent conductive film has a thickness of 10 nm to100 nm and is formed of a material having a refractive index of 1.4 to1.8.
 20. A photoelectric conversion element comprising a transparentsubstrate with a transparent conductive film according to claim 10.